Process of manufacturing pine-oils from wood.



No. 771,859. PATENTED OUT. 11, 1904.

1". s. CLARK a: E. A. HARRIS. PROCESS OF MANUFACTURING PINE 0111s FROMWOOD.

APPLICATION FILED JULY 10, 1903.

2 SHEETS-SHEET 1.

PATENTED OCT. 11, 1904. F. S. CLARK 82: E. A. HARRIS.

PROCESS OF MANUFACTURING PINE OILS FROM WOOD.

APPLICATION FILED JULY 10, 1903.

NO MODEL. 2 SHEETS-SHEET 2.

UNITED STATES Patented October 11, 1904.

PATENT OFFICE.

FRANKLIN S. CLARK AND EDWIN ASOHER HARRIS, OF NEW YORK, N. Y.,ASSIGNORS, BY MESNE ASSIGNMENTS, TO GEORGIA PINE TURPENTINE COMPANY OFNEW YORK, A CORPORATION OF NEIV YORK.

PROCESS OF MANUFACTURING PINE-OILS FROM WOOD.

SPECIFICATION forming part of Letters Patent No. 771,859, dated October11, 1904. Application filed July 10, 1903. Serial No. 165,019. (Nospecimens.)

To all whom it may concern.-

Be it known that we, FRA KLIN S. CLARK and EDWIN 'ASOHER HARRIS,citizens or" the United States, both of the city, county, and

State of New York, have invented a new and useful Process for theManufacture of Pine- Oils from Wood, of which the following is a 4specification.

This invention relates to a process of makro ing water-white pine-oildirectly from the Wood in a continuous series of steps, this oil beingimmediately suitable for all the purposes to which spirits of turpentinemay be applied. The process is further effective in I 5 that such oilsas it produces which are not made water-white by the process are soimproved that the process of refining the same thereafter is madesimpler and easier. What we mean by pine-oil can perhaps be bestexplained by stating that the products of the dry distillation of pineand other similar woods as carried out in the herein process comprise,generally speaking, charcoal, tar, heavy oils, light oils, acetic acid,water, and gases, &c. The heavy oils are heavier than water and containcreosote, parafiin like bodies, &c., together with more or less of thelight oils and acetic acid. The light oils are lighter than Water andconsist of what we call 3 pine-oils, together with more or less of theheavy oils, acetic acid, &c. In the present application the namepine-oils has been used to designate the light oils after they havepassed through the refining treatment de- 3 5 scribed herein. In otherwords, we make the expression pine-oils substantially synonymous withpurified light oils. We are aware that the expression pine-oil has alsobeen used to designate all of the liquid prod- 4 nets ofwood'distillation collectively; but we have not so used it herein.Chemically speaking, pine-oil is a different individual from spirits ofturpentine, although in its practical application it is an excellentsubstitute for turpentine. WVe recognize that pine-wood when distilledat a low temperature with steam will yield a small quantity ofturpentine. These conditions, however, will not yield pine-oils, sincethe initial temperature at which these come over must be considerablyhigher and 5 will vary from about 240 to 300 Fahrenheit.

It is believed that turpentine is an educt of wood, whereas pine-oil isa product. It has been the practice heretofore to produce from the wooddirect only crude pineoils. These oils have been too impure to be usedfor making varnishes or for the other purposes for which spirits ofturpentine is used. It has therefore been necessary heretofore in orderto obtain a pure and marketable product that the crude oil as made atthe retort direct from the wood should be refined by further treatment,necessitating further expense, loss of time, loss of materials due toevaporation, together with the neces- 5 sity of maintaining a refiningand storage plant and other disadvantages incurred by the refiningprocess.

The object of the present invention is to do away with all thesedetrimental features by 7 reducing refined oils direct from the wood inone continuous process.

Our process may, for example, be carried out through the medium of theapparatus shown in the accompanying drawings.

Figure 1 shows a longitudinal sectional view of such an apparatus. Inthis the various pipes and other parts, such as coils and thesuction-pump, are in elevation. Fig. 1 is intended to show one form ofheating means which can be used to heat the retort a, said heating meansconsisting of the furnace A, the fiues B, and the chimney O. In Fig. 1the retort a is only diagrammatically represented, but in practice willbe furnished with heating 5 meansfor example, with the furnace and theother adjuncts shown in Fig. 1*. Fig. 2 is a longitudinal sectional viewof the air-condenser d. Fig. 3 is a transverse section thereof, takenalong the line 3 Sci Fig. 2. Fig. 4 is 9 a longitudinal sectional viewof the tank g, and Fig. 5 is a horizontal sectional view taken along theline 5 5 of Fig. 4.

A retort a is provided with a suitable chargthe condenser is a pipe j,which is of suitable ing-door at the top and a suitable charcoaldoor atthe bottom, these being too evident to need detailed illustration, butare indicated by as and w. The retort a. has a bottom 6/, preferablyconical, and a discharge-pipe (6 leading from the lowermost pointthereof for conducting the tar out of the retort, a steamcoil Z) beingapplied to the said discharge-pipe for the purpose of preventing the tarfrom congealing and to keep it on the move. At the top of the retortthere is provided a pipe 0 for the passage of the vaporized products ofdistillation from the retort. This pipe 0 is in the form of a gooseneckand delivers the vapors from the retort a into an air-condenser, such asd. This air-condenser is a drum or chamber of copper, preferably, havinga central flue 0? leading therethrough for the passage of the air. Fromthe air-condenser d the vapors pass as hereinafter to be described.Arranged in the lower part of the air-condenser (Z is a closedsteam-pipe or coil (V,

which communicates with the steam-supply pipe 6, with which thesteam-coil 6 is connected. Also leading from the steam-supply pipe e isa short pipe 0, which conducts the steam directly into theair-condenser. Pipes (1 and e are respectively provided with valves 6 6The purpose of the condenser d is to fractionatc the products and tothereby separate them for application to different commercial uses, and,further, to more effectively relieve the vapors of heavy oils, aceticacid, &c., in order to secure a finished product of finer quality. Thebottom of the condenser (Z is provided with avalve-controlled discharge(i or other suitable discharge device for drawing off the heavy oils,acetic acid, and water which have been condensed in the condenser (Z.Said condenser (Z is provided with a gage Z to indicate the liquid-leveltherein. Lcadingfrom length and which is preferably formed into acondensing-coilf, from which leads apipe f. The purpose of thecondensing-coil f is to further fractionate the vapors and still furtherrelieve them of heavy oils, acetic acid, &c., the same being condensedand returned from the said coil down the pipe f into the first condenserd. The pipe f enters a tank g and is at its lower end provided with anenlarged portion having in its upper part a great number of minuteperforations, so that the vapor may issue therefrom in numerous smallstreams, and thereby be more intimately brought in contact with suitablealkali, which is contained in the tank. A cheap alkali, like lime,ismost advantageously used in the tank but otherwise any alkali would bejust as effective. From the tank g the vapors pass through the pipe h,which leads into a second tank, 2', which pipe is likewise formed at itslower inner end with an enlarged portion It, provided with minuteperforations, so as to cause the vapor to intimately contact with thealkali ate trap Q2.

in said tank z', which alkali is one of the caustic alkalies, meaningthereby either caustic soda or caustic potash. In order to prevent thecondensation of the vapors in the alkalibath and in order to help thevapors through, and thus prevent the tanks g and from filling up withwater, &c., it is desirable to provide, as shown in the drawings, closedcoils or pipes y'j in said tanks, respectively, and short pipes ornozzles 7c respectively, which open into the tanks 9 and 2". The pipes1'1" and k in lead from the steam-supply pipe 0 and are provided withsuitable valves, as shown, for separately controlling the steam throughsaid pipes. It should be added that the tanks g and@' are preferablycovered on the outside with some non-conducting material I, so as tostill further guard against condensation. Each of the tanks is providedwith gages (indicated by Z Z, respectively) for the purpose ofindicating the liquid-level. Furthermore, each of the said tanks isprovided with a twobranched pipe. The two-branched pipe m for the tank gis provided in each of its branches at 0 with valves for separatelycontrolling them. The branch. n is directed downwardly and 0 upwardly,the latter being for the purpose of receiving the alkali and the branchat for discharging the by-productswhich are formed in the tanks. Thetank i has the pipe on, with branches a 0' for the same purpose.

From the chamber or tank '11 leads a pipe 1), which is provided at itsupper end with a downwardly-turned portion 19, that is formed into acoil 9, forming a condenser, at the lower end of which is an outlet qand an intermedi The products of condensation are barreled off from thedischarge 9'. Gonnected with the downturned portion of the pipe 29 is anupwardly-extending pipe 7', which is formed at its upper end with a coil0 having at its lower end a discharge r and an intermediate trap W. Thispipe r serves as a condenser.

A suitable vacuum-pump s is provided for the purpose of creating asuction in the apparatus and for drawing off the incondensable gases,for which purpose a pipe 25 leads from the pump by means of branch t anda valvecontrolled branch 25 to the condensing-coil 1". This pipe 25 isfurthermore connected by means of branches at and a, the latter beingValvecontrolled, with the condensing-coil q. Not only does this pumpinsure the constant passage of the vapors away from the retort andthrough the apparatus, but it obviates any back pressure on the retort.lVhen not in use for the above purposes, the vacuum-pump also serves forforcing air into the products contained in suitable receptacles in orderto aerate them, or another pump may be kept on hand and used for thispurpose. The vacuum must not be so strong that it overcomes the liquidseals in the traps g and T The vacua in the two condensers q and r canbe varied relatively to each other by manipulating the valves in thepipes a The process is carried out in the apparatus shown as follows:The retort is filled with pine or fir wood or other woods yielding oilsin the nature of pine-oil and then heated gradually. The retort may beheated from a furnace underneath the retort or in any other suitablemanner. The initial temperature at which the pine-oils come over variesfrom about 24:0 to 300 Fahrenheit, depending upon the conditions. Duringthe distillation tar is formed and is best drawn off from the bottom ofthe retort before the heat has become sufliciently high to decompose thetar. This may be accomplished by having the tarpipe (0 always open, sothat the tar runs off from the retort as fast as it is formed. As thewood is heated the vaporized products of drydistillation pass into theair-condenser cl,

into the bottom of which the heavy oils, acetic acid, water, &c.,precipitate, and from here they can be drawn off through the passage (ZIt isadvisable, however, to let them stay a 'short time in the bottom ofthe condenser in order that the heat of the vapors may reevaporate anypine-oils contained therein, which would otherwise be carried off withthe heavy products in case they were withdrawn immediately. However,thebest way to guard against possible loss of pine-oil throughcondensation at this point consists in providing open and closedsteam-pipes e (Z within the condenser (Z, whereby the temperaturetherein can be regulated to prevent condensation of the pine-oil vapors.The open steam-pipe 6 also serves to help along the vapors and to cleanout the apparatus when necessary. The

condensate in the condenser (Z will in actual operations preferably bekept at such level that the live steam from the pipe 0' will play overits surface. vapors pass through the pipe f and preferably, as beforestated, through another condenser, as f, for the purpose of furtherfractionating these vapors to secure a better finished product. Withoutthe condenser f a certain amount of pine-oil might come out dark at theend of the process and require refinement which by the use of saidcondenser would come out white and require no further refinement. Thiscondenser f serves to still further relieve the vapors of heavy oils,acetic acid, &c., which thereupon run back into d.

The uncondensed vapors at this stage of the process and knowncollectively as the light oils consist of pine-oils contaminated withacetic acid, creosote, &c. The vapors passing from the condensingcoil fare conducted by the pipe f into the tank 9, where they are treated withlime or other alkali, air-slaked lime, ash-lye, &c. This lime may be inthe form of milkof lime, the vapors being bubbled through the same, orin dry form. The

From the condenser d the object of the lime is to absorb from the vaporsacetic acid, 620. Acetate of lime is therefore one of the commercialby-products of this process. The lime further absorbs the carbonic-acidgas, and thus improves the quality of the gas, which is one of the finalproducts of this process. The vapor from the tank 9 passes through theconnecting-pipe it into the tank 2', which is filled with caustic sodaor caustic potash. The alkali in the chamber 2' is preferably in theform of a bath through which the vapors are bubbled. Where a solution ofcaustic alkali is used, the strength of the same may vary between widelimits; but a solution of 1.21 specific gravity has been found to givegood results on the average. A by-product is produced in the tank 2',the heavy oils therein combining with the caustic soda and making a finesoluble disinfectant. The vapors thence pass into the pipe 1) and goingthrough the condensing-coil g come out white at the discharge end 9 inliquid form. It is desirable to provide, by means of the pipe 7* or thelike, an air-condenser which is of sufiicient length to condense all thepineoil vapors before said vapors reach the top of this pipe, but not tocondense certain badsmelling oils which are mixed with the pineoils andwhich will contaminate the latter unless they are removed by-fractionalcondensation at this point. These bad-smelling oilsare condensed in theworm-condenser 0- and are drawn off and separated at the discharge end rIt should be said, however, that it is one of the great advantages ofthis process over any other process known to us for producing pine-oilsthat when the same is properly carried out little or no bad-smellingoils are found. Ordinarily, therefore, the fractionating apparatus 1 rcan be dispensed with. It is desirable, however, to have same for useshould these bad-smelling oils for any reason contaminate the pine-oilvapors in appreciable quantity. As the distillation proceeds and theoils become heavier in gravity it is found that the product drawn off atq is lesslikely to hold its white color and tends to become less pure.We have therefore found itdesirable at about this point in the processto collect the heavier oils in separate receivers, these heavier oilsbeing of second quality. It may also be desirable to make a furtherseparation between the oils of still higher gravity and to collect theseseparately as a product of third quality. The following temperatureswere observed in an actual instance of the operation of the process. Thetemperatures in the retort varied from 240 to 800 Fahrenheit, in thedrum (Z from l8et to 220 Fahrenheit, in the lime-chamber from 198 to 212Fahrenheit, and in the soda-chamber from 187 to 212 Fahrenheit. Thesetemperatures in each instance were taken by thermometers suspended inthe vapor, the retort temperature being taken by a thermometer in the.gooseneck 0.

steam were used in the drum (Z.

In the instance given both closed and live Closed steam Was also used inthe lime and soda chambers. Different temperatures from the foregoingwill be shown by different work ings of our process, depending upon theconditions. Thus the temperatures of the different parts of theapparatus will vary, depending upon the kind of wood used and itsquality for example, Whether it is comparatively Wet or dry; also, uponthe size of the retort, the arrangement of the flues about the retort,and the variations in firing; also, upon the location of thethermometers used to measure the temperatures; also, upon Whether thetar is removed in liquid form or distilled from the retort; also, uponwhether an extra fine grade of charcoal is to be produced, inwhich eventthe final temperature in the retort will be run considerably higher thanthat specified-say from 1,000 to 1,200 Fahrenheit; also, upon the amountof live steam introduced, similarly with reference to the amount ofclosed steam used; also, upon the degree of vacuum in case a vacuum-pumpis employed, &c.

It has been found that by pumping air by means of a suitable pump, suchas 8, into the various final products of our process contained insuitable receptacles any remaining traces of bad-smelling oils areremoved. Aeration, furthermore, oxidizes these pine-oils and makes thema still more perfect substitute for turpentine.

It should be understood that caustic alkali alone Without the use oflime (or its equivalent) can be employed in our process with entireeffectiveness. However, as a matter of economy it is desirable to use,as described, lime (or its equivalent) in connection with the causticalkali, thereby preventing the caustic alkali, which is expensive, frombeing used up to remove from the vapors impurities like acetic acid,&c., which can be quite as effectively removed by the lime, &c. In otherwords, in our process the use of successive lime (or its equivalent) andcausticalkali treatments may be substituted for a treatment with causticalkali alone, and it is to be so understood with reference to all theclaims herein calling for caustic alkali alone.

Without restricting ourselves to the apparatus shown or to the processas described or enumerating all equivalents, as some steps in theprocess may be used without or replaced by others, what we claim is 1.The process substantially as herein described for preparing pine-oilsand pine-like oils, which consists in subjecting the wood todistillation and treating the vapors containing said oils with causticalkali under such temperature conditions that said oils are treated invapor form.

2. The process substantially as herein described for preparing pine-oilsand pine-like oils, which consists in subjecting the wood todistillation and treating the light oil-vapors with caustic alkali undersuch temperature conditions that said oils are treated in vapor form.

3. The process substantially as herein described for preparing pine-oilsand pine-like oils, which consists in subjecting the wood todistillation, subjecting the vapors to fractional condensation therebycondensing vapors that are condensable Without causing condensation ofthe pine-oil vapors, treating the residual vapors containing saidpine-oils with caustic alkali under such temperature conditions thatsaid oils are treated in vapor form, and'condensing the ultimate vapors.

4. The process substantially as herein described for preparing pine-oilsand pine-like oils, which consists in subjecting the Wood todistillation, removing the tar in liquid form from the retort, treatingthe vapors containing said oils With caustic alkali under suchtemperature conditions that said oils are treated in vapor form, andcondensing the ultimate vapors.

5. The process substantially as herein described for preparing pine-oilsand pine-like oils, which consists in subjecting the wood todistillation, removing the tar in liquid form from the retort,subjecting the vapors to fractional condensation thereby condensingvapors that are condensable without causing condensation of the pine-oilvapors, treating the residual vapors containing said pine-oils withcaustic alkali under such temperature conditions that said oils aretreated in vapor form, and condensing the ultimate vapors.

6. The process substantially as herein described for preparing pine-oilsand pine-like oils, which consists in subjecting the wood todistillation, subjecting the vapors to fractional condensation therebycondensing vapors that are condensable without causing condensation ofthe pine-oil vapors, regulating the heat during such condensation tokeep said pineoils vaporized, treating the residual vapors with causticalkali under such temperature conditions that said oils are treated .invapor form, and condensing the ultimate vapors.

7 The process substantially as herein described for preparing pine-oilsand pine-like oils, which consists in subjecting the Wood todistillation, subjecting the vapors to fractional condensation therebycondensing vapors that are condensable Without causing condensation ofthe pine-oil vapors, introducing live steam during such condensation,treating the residual vapors with caustic alkali under such temperatureconditions that said oils are treated in vapor form, and condensing theultimate vapors.

8. The process substantially as herein described for preparing pine-oilsand pine-like oils, which consists in subjecting the wood todistillation, removing the tar in liquid form from the retort,subjecting the vapors to fractional condensation thereby condensingvapors that are condensable without causing condensation of the pine-oilvapors, introducing live steam during such condensation, treating theresidual vapors with caustic alkali under such temperature conditionsthat said oils are treated in vapor form, and condensing the ultimatevapors.

9. The process substantially as herein described for preparing pine-oilsand pine-like oils, which consists in subjecting the wood todistillation, removing the tar in liquid form from the retort,condensing from the vapors the bulk of the heavy oils, treating theresidual vapors containing said pine-oils with caustie alkali under suchtemperature conditions that said oils are treated in vapor form, andcondensing the ultimate vapors.

10. The process substantially as herein described for preparingpine-oils and pine-like oils, which consists in subjecting the wood todistillation, condensing the bulk of the tar and heavy oils from thevapors, treating the residual vapors containing said pine-oils withcaustic alkali under such temperature conditions that said oils aretreated in vapor form, and condensing the ultimate vapors.

11. The process substantially as herein described for preparingpine-oils and pine-like oils, which consists in subjecting the wood todistillation, treating the vapors containing said oils with causticalkali under such temperature conditions that said oils are treated invapor form,and separating by fractional condensation the bad-smellingoils from the pine-oils.

12. The process substantially as herein described for preparingpine-oils and pine-like oils, which consists in subjecting the wood todistillation, subjecting the vapors to fractional condensation therebycondensing vapors that are condensable without causing condensation ofthe pine-oil vapors, treating the residual vapors containing saidpine-oils with caustic alkali under such temperature conditions thatsaid oils are treated in vapor form, and separating by fractionalcondensation the bad-smelling oils from the pine-oils.

13. The process substantially as herein described for preparingpine-oils and pine-like oils, which consists in subjecting the wood todistillation, treating the vapors containing said oils with causticvalkali under such temperature conditions that said oils are treated invapor form, condensing the residual vapors, and aerating the condensedproduct.

14. The process substantially as herein described for preparingpine-oils and pine-like oils, which consists in subjecting the wood todistillation, subjecting the vapors to fractional condensation therebycondensing vapors that are condensable without causing condensation ofthe pine-oil vapors, treating the residual vapors containing saidpine-oils with caustic alkali under such temperature conditions thatsaid oils are treated in vapor form, condensing the ultimate vapors, andaerating the condensed product.

15. The process substantially as herein described for preparingpine-oils and pine-like oils, which consists in subjecting the wood todistillation and treating the vapors containing said oils with an alkalicapable of removing from the vapors acetic acid and creosote, under suchtemperature conditions that said oils are treated in vapor form.

16. The process substantially as herein described for preparingpine-oils and pine-like oils, which consists in subjecting the wood todistillation, treating the vapors containing said oils first with analkali capable of removing acetic acid from the vapors and thereafterwith another alkali capable of removing creosote from the vapors, thetemperature conditions being such that said oils are treated in vaporform.

17. The process substantially as herein described for preparingpine-oils and pine-like oils, which consists in subjecting the wood todistillation, subjecting the vapors to fractional condensation therebycondensing vapors that are condensable without causing condensation ofthe pine-oil vapors, treating the residual vapors containing saidpine-oils with an alkali capable of removing from the vapors acetic acidand creosote under such temperature conditions that said oils aretreated in vapor form, and condensing the ultimate vapors.

18. The process substantially asherein described for preparing pine-oilsand pine-like oils, which consists in subjecting the wood todistillation, subjecting the vaporsto fractional condensation therebycondensing vapors that are condensable without causing condensation ofthe pine-oil vapors, treating the residual vapors containing said oilsfirst with an alkali capable of removing acetic acid from the vapors andthereafter with another alkali capable of removing creosote from theVapors, the temperature conditions being such that said oils are treatedin vapor form, and condensing the ultimate vapors.

19. The process substantially as herein described for preparingpine-oils and pine-like oils, which consists in subjecting the wood todistillation and treating the light oil-vapors with an alkali capable ofremoving from the vapors acetic acid and creosote under such temperatureconditions that said oils are treated in vapor form.

20. The process substantially as herein described for preparingpine-oils and pine-like oils, which consists in subjecting the wood todistillation and treating the light oil-vapors with an alkali capable ofremoving acetic acid from the vapors and thereafter with another alkalicapable of removing creosote from the vapors, the temperature conditionsbeing such that the pine-oils are treated in vapor form.

IIO

r 21. The process substantiallyas herein described forpreparingpine-oils and pine-like -o1ls,--Which consists in sub ecting the wood todistillation, removing tar in liquid form from the-retort, Sub ectingthe vapors to fractional condensation thereby condensing vapors that arecondensable without causing condensation of the pine-oil vapors,treating the vapors containing said pine-oils with lime under suchtemperature conditions that said oils are treat- -ed in'vapor form, andcondensing the ultimate vapors.

= 22. The process substantially as herein described-forpreparingpine-oils and pine-like oils, which consists'in subjecting the wood to 1distillation, subjecting the vapors to fractional condensation'therebycondensing vapors that are condensable without causing condensation ofthe pine-oil vapors treating I the residual vapors containingsaidpine-oils with lime un- "der-suchtemperature conditions that said oilsare treated in vapor form, and condensing the ultimate vapors.

The process substantially asherein dewitnesses.

' FRANKLIN S. CLARK.

EDWIN ASCHER HARRIS. WVitnesses to the signature of Franklin S. Clark:

G. Gr. MYRovER. \VALTER HALL.

Witnesses to the signature of Edwin Ascher Harris:

GEO. L. VVHEELoeK, E- W. SoHERR, Jr.

